NZ206490A

NZ206490A - Fungicidal compositions containing hydroxyalkylazoles

Info

Publication number: NZ206490A
Application number: NZ206490A
Authority: NZ
Inventors: H-L Elbe; K H Buchel; W Brandes; P Reineck; H-J Rosslenbroich
Original assignee: Bayer Ag
Priority date: 1982-12-09
Filing date: 1983-12-06
Publication date: 1986-07-11
Also published as: PT77758B; AU2191383A; CA1228537A; AU562753B2; EP0111234A2; DK565283D0; ZA839138B; JPS59112904A; HU193888B; EP0111234A3; ATE22649T1; DE3245504A1; BR8306749A; DE3366651D1; US4584308A; EP0111234B1; IL70389A0; GR79746B; IL70389A; TR22774A

Abstract

A method of combating fungi which comprises to such fungi or to a fungus habitat a fungicidally effective amount of a substituted hydroxyalkyl-azole of the formula <IMAGE> (I) in which R1 is optionally substituted phenyl, -O-phenyl, -S-phenyl, -SO-phenyl, -SO2-phenyl, -CH2-phenyl, -CH2-O-phenyl, -CH2-S-phenyl, -CH2-SO-phenyl or -CH2-SO2-phenyl, R2 is alkyl, R3 is alkyl, X is a nitrogen atom or the CH group, Y is halogen, alkyl, cycloalkyl, alkoxy, alkylthio, halogenoalkyl, halogenoalkoxy, halogenoalkylthio, optionally substituted phenyl, optionally substituted phenylalkyl or optionally substituted phenylalkoxy, and m is 0, 1, 2 or 3, or an addition product thereof with an acid or metal salt.

Description

<div class="application article clearfix" id="description"> New Zealand Paient Spedficaiion for Paient Number £06490 Priority Date(s): Complete Specification Filed: . iv< ."&3. Class: ACt!(ik&J.SQ,&b Publication Date: .. x 3. JUL 1986. P.O. Journal, No: .../o?£T. NORflcsiii 206490 N.Z.No. NEW ZEALAND Fatents Act 3953 COMPLETE SPECIFICATION "FUNGICIDAL AGENTS, THEIR PREPARATION AND THEIR USE." We, BAYER AKTIENGESELLSCHAFT, a Company registered under the laws of the Federal Republic of Germany, of Leverkusen, Germany, do hereby declare the invention, for which we pray that a Patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement : - (Followed by 1A.) - ie- 206490 The present invention relates to the use of substituted hydroxyaIkyl-azoles as fungicidal agents. It has already been disclosed that certain hydroxya Ikyl-azole derivatives have good fungicidal pro- 5 perties (compare European Patent Specifications 0,019,190, 0,029,542 and 0,040,345, and New Zealand Patent Specification 193,745). 10 However, the action of these compounds is not always completely satisfactory when low amounts and concentrations are applied. It has been found that the substituted hydroxy-alkyl-azoles of the general formula r2 oh v,n 15 R1 - C - i -O CI) i , I 3 ch2 I in which R^ represents in each case optionally substituted phenyl, -0-phenyl, -S-phenyl, -SO-phenyl, -SOg-phenyl, -CH2-phenyl, -CH2~0-phenyI, 20 -CH2-S-pheny l# -CH2"SO-phenyI or -CH2-SO2- pheny I, R^ represents alkyl, r3 represents alkyl, X represents a nitrogen atom or the CH group, 25 Y represents halogen, alkyl, cycloalkyl, alkoxy, alkylthio, halogenoalkyI, halogenoaIkoxy, halo-genoa Iky Ithio, optionally substituted phenyl, optionally substituted phenoxy, optionally substituted phenylalkyl or optionally substituted : i ■ V f 16IWI986-;; v> V' TV > 206490 - 2 - pheny La Lko xy and m represents the number 0, 1, 2 or 3, and acid addition salts and metal salt complexes thereof/, have good fungicidal properties. 5 The compounds of the formula (I) have an asym metric carbon atom and can therefore be obtained in the two optical isomer forms. Surprisingly, the substituted hydroxya I ky l-azoLes of the formula (I) to be used according to the invention 10 exhibit a better fungicidal activity than the hydroxy-alkylazolyl derivatives which are already known from the prior art and are closely related compounds structurally and from the point of view of their action. The use, according to the invention, of the new substances thus 15 represents an enrichment of the art. Formula (I) provides a general definition of the substituted hydroxya Iky l-azoles to be used according to the invention. Preferably, in this formula/ R^ represents phenyl, -Cf^-phenyl, -CH2~0-pheny1/ 20 -CH2~S-phenyI/ -CH2~S0-phenyI or -CH2~S02~pheny 1/ in each case mono- or di-substituted by identical or different substituents, preferred substituents on the phenyl which may be mentioned being the meanings of Y; 25 R2 represents straight-chain or branched alkyl with 1 to 4 carbon atoms; R3 represents straight-chain or branched alkyl with 1 to 4 carbon atoms; X represents a nitrogen atom or the CH group; .s' 30 Y represents halogen, alkyl with 1 to 4 carbon atoms, cycloalkyl with 5 to 7 carbon atoms, alkoxy or alkylthio with in each case 1 to 4 carbon atoms, halogenoaIky I, halogenoaIkoxy or halogenoalkylthio with in each case 1 or 2 carbon 35 atoms and 1 to 5 identical or different halogen atoms, such as, preferably/ fluorine and chlorine k. H gg 060 2 06490 - 3 - atoms, or phenyl, phenoxy or phenyLaLkyL or phenylalkoxy with 1 or 2 carbon atoms in the aLkyl part or in the alkoxy part, each of which is optionally substituted by halogen or alkyl 5 with 1 or 2 carbon atoms; and m represents the number 0, 1, 2 or 3. Moreover, preferably, in formula CI), R1 represents -0-phenyl, -S-phenyl, -SO-phenyl or -S02~Pheny I, in each case mono- or di-sub-10 stituted by identical or different substituents, preferred substituents on the phenyl which may be mentioned being the meanings of Y; represents straight-chain or branched alkyl with 1 to 4 carbon atoms; 15 R3 represents straight-chain or branched alkyl with 1 to 4 carbon atoms; X represents a nitrogen atom or the CH group; Y represents halogen, alkyl with 1 to 4 carbon atoms, cycloalkyl with 5 to 7 carbon atoms, 20 alkoxy or alkylthio with in each case 1 to 4 carbon atoms, ha logenoaLkyL, ha logenoaIkoxy or haLogenoaLkyIthio with in each case 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, such as, preferably, fluorine and chlorine 25 atoms, or phenyl, phenoxy or phenylalkyl or phenylalkoxy with 1 or 2 carbon atoms in the aLkyl part or in the alkoxy part, each of which is optionally substituted by halogen or aLkyl with 1 or 2 carbon atoms; and 30 m represents the number 0, 1, 2 or 3. Particularly preferred compounds of the formula CI) are those in which R^ represents phenyl, -CHg^phenyI, -C^-O-phenyL, 35 -CH2~S-phenyI, -CH2~S0-phenyL or -CH2~S02~phenyI, in each case mono- or di-substituted by identical or different substituents, preferred substituents on the phenyl which may be mentioned being the meanings of Y; R represents methyl or ethyl; 5 R3 represents methyl or ethyl; X represents a nitrogen atom or the CH group; Y represents fluorine, chlorine, bromine, methyl, isopropyl, tert.-butyl, cyclohexyl, methoxy, methylthio, trifluoromethy I, trif I uoromethoxy or 10 trifIuoromethy1thio, or phenyl, phenoxy, benzyl or benzyloxy which is optionally substituted by fluorine, chlorine or methyl; and m represents the number 0, 1 or 2. Particularly preferred compounds of the formula 15 (I) are, moreover, those in which represents -0-phenyl, -S-phenyl, -SO-phenyl or -SOg-phenyl, in each case mono- or di-sub-stituted by identical or different substituents, preferred substituents on the phenyl which may be mentioned being the meanings of Y; R^ represents methyl or ethyl, R3 represents methyl or ethyl; X represents a nitrogen atom or the CH group; Y rep resents fluorine, chlorine, bromine, methyl, isopropyl, tert.-butyl, cyclohexyl, methoxy, methylthio, trifluoromethyl, trifluoromethoxy or trifluoromethylthio, or phenyl, phenoxy, benzyl or benzyloxy which is optionally substituted by fluorine, chlorine or methyl, and m represents the number 0, 1 or 2. Addition products of acids and those substituted hydroxyaIkyl-azoles of the formula CI) in which the substituents R^, R^, R3, X and Ym have the meanings 35 which have already been mentioned as preferred for these substituents are also preferred compounds according to 20 25 30 ^ _5 206490 the invention. Preferred acids which can be added on include hydrogen halide acids, such as, for example, hydrochloric acid and hydrobromic acid, especially hydrochloric acid, 5 and furthermore phosphoric acid, nitric acid, monofunc-tional and bifunctional carboxylic acids and hydroxy-carboxylic acids, such as, for example, acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid and lactic acid, 10 and sulphonic acids, such as p-toluenesuIphonic acid and 1,5-naphthalenedisu Iphoni c acid. Addition products of salts of metals of main groups II to IV and of sub-groups I and II and IV to VIII and those substituted hydroxyalkyl-azoles of the formula 15 (I) in which the substituents R ^ , R ^ , R 3 , X and Ym have the meanings which have already been mentioned as preferred for these substituents are also preferred compounds according to the invention. In this context, salts of copper, zinc, manganese, 20 magnesium, tin, iron and nickel are particularly preferred. Suitable anions of these salts are those which are derived from acids leading to physiologically acceptable addition products. Particularly preferred acids of this type are, in this connection, the hydrogen halide 25 acids, such as, for example, hydrochloric acid and hydrobromic acid, nitric acid and sulphuric acid. The following compounds of the formula (I) may be mentioned specifically, in addition to the compounds mentioned in the preparation examples (X represents 30 either a nitrogen atom or the CH group): r2 oh CI) r3 c h 2 u LI 2 0 64 90 n1 ** y a I 0 1 . <9> U. C«3 ch3 2-Cl $ 0 1 ch3 ch3 2-Cl ei-©-o- ^ CI ch, ch3 3-Cl ch3 ch3 3,4-Cl2 • o I ch, ch3 .3-Cl cw;G/-o- chs CHj 3-CI ch3 ch3 2„4-Cl2 1 o 41 u. ch3 ch3 2#4-Cl2 1 o $ u ch3 CH3 3#4-Cl2 1 o § u ch3 CH3 2-chs,4-Cl °" ch3 CH3 3*4-Cl2 • 1 o u. C«3 CH3 2-ch3,4-Cl 1 o mJ u CH 3 ' ch3 2-Cl & 0 1 • CH 3 ch3 2-Cl 1 o u CH3 ch3 4-Cl «i-@— ch5 ch3 2,4-ClZ il a aa 06a. - 7 - 2 0 6490 ci CL ^0- CI 0- CL-(O/-0- Cl Q- 0-Cl - 0- F- -0- Ct- Cl CI 0- CL CL 0- d-1- <s£°- 'F.o. CHj CHj CHj CHj CHj CHj CHj CHj CHj CHj CHj CHj CHj CHj CHj CHj CHj CHj CHj CH 3 CHj CHj CHj CHj CHj CHj CHj CHj CHj CHj 2-Cl 4-F 4-F *-©■» 4-0-^^-Cl 4-Cl 2-F 2-F 2-F 2,4—C12 2,4-Ctj 4—CI - 8 - 2064-9 0 <-©— ©:- CI s- Cl l-©- ^s- -©-s* ^s-<■-©>■s_ -<£>s- -<0>~s* ^s- .ci s- c^ls- /-^rCL CI-®* S- RZ R3 T n CHj CHj 2-Cl CHj CHj 2-Cl CHj CHj 3-Cl CHj CHj 3,4-Cl2 CHj CHj 3-Cl CHj CHj 3-Cl CHj CHj 2,4-Cl2 CHj CHj 2,4-Cl2 CHj CHj 3,4-Cl2 CHj CHj 2-CHj,4-CI CHj CHj 3,4-Cl2 CHj CHj 2-CHj,4-CI CHj CHj 2-Cl CHj CHj 2-Cl CHj CHj 4-Cl CHj CHj 2*4-Cl2 1 5 ,ci s- 5 ei-©-s- ,ci s- Cl CI- -s« F CL -CH- -©"s* ,ci 10 >-s- cl ■ s< qs--- .F - 9 - 206490 ** R' T nl CHS CH3 2-CL CH, CH, 4-F CH3 CHj • 4-F CHj CHj *-©-« CHj CHS CHj CHj CHj CHj CH, CHj ch3 CHj 4-Cl CHj CH3 2-F CHj CHj 2-F CHj CHj 2-F CHj CH3 2,4-Cl2 CH3 CH3 2*4-Cl2 CHS CH, 4-Cl ■Le-' A -0D 06fr 10 15 '•Of- CH!' CHj. CI -CHj" cl —c h 2" cl ch2- «2- l-©- CH*' I"©" CHr — ^h2" I"©" CHr CI ch2-ei-^- ch2- - 10 -** 2 0 64 9 0 R3 CL ch3 ch3 2-CL ch3 CHj 2-CL ch3 CHj 3-CL ch3 CH 3 3,4-clj ch3 ch3 3-CL ch3 ch3 3-CL ch3 CHj 2,4-Clz ch3 CHj 2,4-CLz ch3 CHj 3,4—c L 2 ch3 CHj 2-CH3,4-Cl ch3 CHj 3,4—c L 2 ch3 CHj 2-chj,4-cl ch3 CHj 2-CL ch3 CHj 2-cl ch3 CHj 4-Cl CHj CHj 2,4-Cl2 WTTTtWf et-©-™,- CI ch2- CKO>CH2- ,Cl ch 2" F-<y>-CH2-Cl-©-CH«- .Cl ch2-CL-^^—ch2" ch2- crHi* <g>W 'f.ch2- - 11 - 2064 9 0 CHj CH 3 2-CL CHj CHj 4-F CHj CHj 4-F CHj CHj CHj CHj CHj CHj CHj CHj CHj CHj 4-0-^^-Cl CHj ch3 4-CL CHj CHj 2-F CHj CHj 2-F chj CHj 2-F CHj CHj 2,4-C L 2 CHj CHj 2#4-CI2 CHj CHj 4-Cl <3>- CL cl /—f Cl ■<o>- CI k CL - 12 - 2 O649 Q m CHj CHj 2-CL CHJ CHj 2-CL CHj CHj 3-CL CHj CHj 3,4-CLz CHj CHj 3-CL CHj CHj 3-CL CHj . CHj 2,4-CL 2 CHj CHj 2,4-CI2 CHj CHj 3/4-C I 2 CHj CHj 2-CHj,4-CL CHj CHj 3,4-C L 2 CHj CHj 2-CHj,4-CL CHj CHj . 2-CL CHj CHj 2-CL CHj CHj 4-CL CHj CHj 2,4-C L2 -CI ,Cl Cl-W CI "■CP <^1 0, - 13 - 2 0 64 9 q R1 R2 C I CH3 ch3 2-CL CH3 ch3 4-F CH3 chs 4-F CH3 chs CH3 ch3 CH3 ch3 CHj chs CHj ch3 *-0-©- chs chs 4-CL CH3 ch3 2-F ch3 chs 2-F ch3 ch3 2-F ch3 ch3 2,4-C I 2 CHs ch3 2,4-C L 2 CHj ch3 4-Cl «^1 CI -©■ CHS CH3 4-0-((J>-Cl ,Cl 206490 - 14 - The active compounds to be used according to the invention are not yet known. However, they are the subject of an earlier Patent Application which has been filed by the Applicant Company and has not yet been pub- 5 lished (compare European Patent Specification 0,090,993), and are obtained by a process in which oxiranes of the formula in which 10 r^, r^/ r3, y and m have the abovementioned meaning, are reacted with azoles of the formula ,x =r, (iii) m - n j V-it n in which 15 X has the abovementioned meaning and M represents hydrogen or an alkali metal, preferably sodium or potassium, in the presence of an inert organic solvent, such as, for example, alcohols, and if appropriate in the presence of 20 a base, such as, for example, alkali metal alcoholates, at temperatures between 60 and 150°C, and, if appropriate, the resulting hydroxyaIkyl-azoles of the formula r2 oh / m «*-S-<CHj)nc - C (la) >T * r3 ch ? I "^X (. in which 25 \c, R, X, Y and m have the abovementi oned,/^*" (y 1 6 may i986 Ov - 15 - meani ng, R^ represents optionally substituted phenyl and n represents the number 0 or 1, are oxidised by known methods in the customary manner. 5 If 1 mol of oxidising agent, such as m-chloroper* benzoic acid in methylene chloride or hydrogen peroxide in acetic anhydride* is used at temperatures between -30 to +30°C, the compounds of the formula (I) according to the invention with the -SO- grouping are preferentially 10 formed. With an excess of oxidising agent and higher temperatures (10 to 80°C), the compounds of the formula (I) according to the invention with the -SOg- grouping are preferentially formed. The oxidation products are isolated in the customary manner. 15 The oxiranes of the formula (II) are not yet known. They are also the subject of the abovementioned earlier Patent Application which has been filed by the ADDlicant Company and has not yet been published (compare European Patent Specification 0,090,993), and are obtained by a process in which ketones of 20 the formula r2 f - C - CO R3 -<eT m (iv) in wh i ch R , R , R , Y and m have the abovementioned 25 meaning, either C() are reacted with dimethyloxosulphonium methylide of the formula 6+c- <CH3)2SOCH2 (V) 30 in a manner which is in itself known, in the presence of I'16 MAY 1986 . V 1 '/ A '■ 4 o -4* \.v . ■ - 16 - a diluent, such as, for example, dimethyIsu Iphoxide, at temperatures between 20 and 80°C (in this context, compare the statements in J . Am. Chem. Soc. 87_, 1363-1364 (1965)), or 5 fl) are reacted with t r i met hy I su Ip honi um methyl-sulphate of the formula r <+n (- > [CCH3)3S j CH3SO4 CVI) in a manner which is in itself known, in the presence of an inert organic solvent, such as, for example, aceto-10 nitrile, and in the presence of a base, such as, for example, sodium methylate, at temperatures between 0 and 60°C, preferably at room temperature (compare also the statements in Heterocycles 8, 397 (1977)). The acid addition salts of the compounds of the 15 formula (I) can be obtained in a simple manner by customary salt formation methods, for example by dissolving a compound of the formula (I) in a suitable inert solvent and adding the acid, for example hydrochloric acid, and they can be isolated in a known manner, for example by 20 filtration, and if appropriate purified by washing with an inert organic solvent. The metal salt complexes of compounds of the formula (I) can be obtained in a simple manner by customary processes, thus, for example, by dissolving the metal 25 salt in alcohol, for example ethanol, and adding the solution to the compounds of the formula (I). The metal salt complexes can be isolated in a known manner, for example by filtration, and if appropriate purified by recrystal-li sati on. 30 The active compounds to be used according to the invention exhibit a powerful microbicidal action and can be employed in practice for combating undesired microorganisms. The active compounds are suitable for use as plant protection agents. 2Ot49 0 - 17 - Fungicidal agents in plant protection are employed for combating Plasmodiophoromycetes, Oomycetes, Chytridio-niycetes. Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes. The good toleration, by plants, of the active compounds, at the concentrations required for combating plant diseases, permits treatment of above-ground parts of plants, of vegetative propagation stock and seeds, and of the soil. As plant protection agents, the active compounds according to the invention can be used with particularly good success for combating Sphaerotheca species, such as against the powdery mildew of cucumber causative organism (Sphaerotheca fuliginea), cereal diseases, such as against the stripe disease of barley causative organism (Drech-slera graminea) or against the brown spot disease on wheat causative organism (Leptosphaeria nodorum), and rice diseases, such as Pyricularia oryzae and Pe 11 icuI aria sasakii. When applied in appropriate amounts, the active compounds according to the invention also exhibit plant growth-regulating and selective herbicidal properties. The active compounds can be converted to the customary formulations, such as solutions, emulsions, we 11-able powders, suspensions, powders, dusting agents, foams, pastes, soluble powders, granules, aerosols, suspension-emulsion concentrates, seed treatment powders, natural and synthetic materials impregnated with active compound, very fine capsules in polymeric substances and in coating compositions for seed, and formulations used with burning equipment, such as fumigating cartridges, fumigating cans, fumigating coils and the like, as well as ULV cold mist and warm mist formulations. These formulations are produced in known manner, for example by mixing the active compounds with extenders, that is, liquid solvents, liquefied gases under pressure, hi A 00 Oil - 18 - and/or solid carriers/ optionally with the use of surface-active agents, that is, emulsifying agents and/or dispersing agents, and/or foam-forming agents. In the case of the use of water as an extender, organic solvents 5 can, for example, also be used as auxiliary solvents. As liquid solvents, there are suitable in the main: aromatics, such as xylene, toluene or alkyl naphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as ch lorobenzenes, chIoroethy lenes or methylene 10 chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyc lohexanone, strongly polar 15 solvents, such as dimethy Iformamide and dimethyIsu lphoxide, as well as water; by liquefied gaseous extenders or carriers are meant liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons as well 20 as butane, propane, nitrogen and carbon dioxide; as solid carriers there are suitable: for example ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmori I lonite or diatomaceous earth, and ground synthetic minerals, such as highly-dispersed 25 silicic acid, alumina and silicates; as solid carriers for granules there are suitable: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of 30 organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; as emulsifying and/or foam-forming agents there are suitable: for example non-ionic and anionic emulsifiers, such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for 35 example alkylaryl polyglycol ethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as well as albumin - 19 - ^ hydroLysation products; as dispersing agents there are suitable: for example lignin-sulphite waste liquors and methylcellulose. Adhesives such as carboxymethyIceIluIose and 5 natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, can be used in the formulations. It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and 10 Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phtha I ocyanine dye-stuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc. The formulations in general contain between 0.1 15 and 95 per cent by weight of active compound, preferably between 0.5 and 90%. The active compounds according to the invention can be present in the formulations or in the various use forms as a mixture with other known active compounds, 20 such as fungicides, bactericides, insecticides, acari-cides, nematicides, herbicides, bird repellants, growth factors, plant nutrients and agents for improving soil structure. The active compounds can be used as such or in 25 the form of their formulations or the use forms prepared therefrom by further dilution, such as ready-to-use solutions, emu Is ions, suspensions, powders, pastes and granules. They are used in the customary manner, for example by watering, immersion, spraying, atomising, 30 misting, vaporising, injecting, forming a slurry, brushing on, dusting, scattering, dry dressing, moist dressing, wet dressing, slurry dressing or encrusting. In the treatment of parts of plants, the active compound concentrations in the use forms can be varied 35 within a substantial range. They are, in general, between 1 and 0.0001% by weight, preferably between 0.5 and 10 2 0 64 9 0 - 20 -0.001%. In the treatment of seed, amounts of active compound of 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, are generally required. For the treatment of soil, active compound concentrations of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02% by weight, are required at the place of action. Preparation Examples Example 1 CHj OH - \ \ -(o)-« w chj ^h2 ■N' O 30 g (0.0935 mol) of 2-(4-chIorophenyI)-2-(4-chlorophenyl-tert.-butyl)-oxirane in 40 ml of n-propanol are added dropwise to a solution of 7.7 g (0.108 mol) of sodium imidazole in 60 ml of n-propanol at the reflux 15 temperature. The reaction mixture is subsequently stirred under reflux for 48 hours and cooled, water is added and the mixture is extracted with methylene chloi— ide. The organic phase is dried over sodium sulphate and concentrated in vacuo. The oily residue is stirred into 20 diisopropyl ether. The resulting crystalline precipitate is filtered off with suction and dried. 12.7 g (35% of theory) of 2,4-bis-(4-ch loropheny l)-3,3-dimethyl-1-(imidazo 1-1-yI)-2-butano I of melting point 174°C are obtained. 2 5 fLr®Pa.rjit_i°H £f_th^e_s^a_rt_i_n^ .subst^ajnce^ CHj / "C - A"-®"" CM1 0 — CM* A solution of 59.2 g (0.47 mol) of dimethyl dQc 4 9 q - 21 - sulphate and 32 g (0.517 mol) of dimethyl sulphide in 270 ml of acetonitrile is stirred at room temperature for 5 days. a solution of 81.5 g (0.2655 mol) of 4-chloro-phenyl 4-ch lorophenyl-tert.-butyl ketone in 80 ml of 5 acetonitrile is then added dropwise at 20 to 25°C in the course of about 2 hours. 28.7 g (0.53 mol) of sodium methylate are added at the same temperature. The entire reaction mixture is subsequently stirred for 12 hours and is then concentrated in vacuo. The residue is stirred 10 overnight with a mixture of 200 ml of ethyl acetate and 150 ml of water. The organic phase is separated off, dried over sodium sulphate and concentrated in vacuo. 72.6 g (85.2% of theory) of crude 2-(4-ch loropheny l)-2-(4-ch lorophenyI-1ert.-butyI)-oxirane are obtained and 15 are further reacted directly. cn3 ci-0>-ch2 - cj - co -^-ci ch3 85 g (0.466 mol) of 4-chlorophenyI isopropyl ketone, 31.3 g (0.56 mol) of potassium hydroxide and 5 g of tetrabutyLammonium bromide in 120 ml of toluene are 20 heated to the reflux temperature, and a solution of 75 g (0.466 mol) of 4-ch IorobenzyI chloride in 60 ml of toluene is added dropwise. The reaction mixture is subsequently stirred under reflux for 12 hours, cooled and washed with water and the organic phase is dried over sodium sulphate 25 and concentrated in vacuo. 81.5 g (60% of theory) of 4-chlorophenyl 4-chloropheny l-tert.-butyl ketone of refractive index n^® 1.5711 are obtained. ku * 00 BiW j <n- - 22 - Example 2 £ u ■ 4 9 0 CHt OH 1 * { CHj CH2 rrM^ N U HCl A solution of 30 g (0.093 mol) of 2-(4-chloro-phenyl)-2-C2-(p-chlorophenoxy)-prop-2-yl3-oxi rane in 5 40 ml of n-propanol is added dropwise to a solution of 7.6 g (0.107 mol) of sodium 1,2,4-triazole in 60 ml of n-propanol at room temperature. The reaction mixture is subsequently stirred at the reflux temperature for 48 hours and is cooled, water is added and the mixture is 10 extracted with methylene chloride. The organic phase is dried over sodium sulphate and concentrated in vacuo. The oily residue is purified by column chromatography. 6.7 g (18.4% of theory) of 3-(4-ch lorophenoxy)-2-(4-chlorophenyl)-3-methyl-1-(1,2,4-triazol-1-yl)-2-butanol 15 are obtained. This product is stirred with 20 ml of saturated hydrogen ch loride/ether solution at room temperature. The precipitate which has separated out is filtered off with suction, rinsed with a little ether and dried at 40°C in vacuo. 6.5 g (89% of theory, based on 20 the base employed) of 3-(4-chlorophenoxy)-2-(4-chloro-phenyl)-3-methyl-1-(1,2,4-triazol-1-yl)-2-butanol hydrochloride of melting point 135°C are obtained. P/_e p^r_a t J_o ri £f_t h^e_sjt a_r t_i_njj £ub^s_t ajn c CHS 0- —CHj 25 A solution of 59.2 g (0.47 mol) of dimethyl sulphate and 32 g (0.517 mol) of dimethyl sulphide in 270 ml of acetonitrile is stirred at room temperature for r - : 4 9 0 23 5 days. A solution of 87 g of 4-chlorophenyl 2-(p-chloro-phenoxy)-prop-2-yI ketone in 80 ml of acetonitrile is then added dropwise at 20 to 25°C in the course of about 2 hours. 28.7 g (0.53 mol) of sodium methylate are intro-5 duced at the same temperature, and the mixture is subsequently stirred for 12 hours and then concentrated. The residue is stirred overnight with a mixture of 200 ml of ethyl acetate and 150 ml of water. The organic phase is separated off, dried over sodium sulphate and concentra-10 ted in vacuo. 49 g (76% of theory) of crude 2-C4-chloro-phenyl)-2-C2-(p-chlorophenoxy)-prop-2-yl3-oxirane are obtained, and are further reacted directly. 15 (0.3982 mol) of potassium carbonate in 400 ml of toluene are heated under reflux for 2 hours, using a water separator. The mixture is cooled to 40°C and a solution of 2-bromo-prop-2-y I 4-chlorophenyl ketone in 170 ml of toluene is added dropwise. This reaction mixture is sub-20 sequently stirred at 100°C for 5 hours and is then cooled, water is added and the organic phase is separated off. This phase is washed with dilute sodium hydroxide solution and water, dried over sodium sulphate and concentrated. 87 g (85% of theory) of crude 4-chlorophenyl 2-(p-25 chlorophenoxy)-prop-2-yl ketone are obtained and are further reacted directly. ch j Br- c - co - ®-Cl ch3 1 ml of hydrogen bromide/gI acia I acetic acid is added to 65.5 g (0.36 mol) of 4-chlorophenyl isopropyl 30 ketone in 200 ml of chloroform, and 57.5 g (0.36 mol) of Lf'R LL UUB <?H3 52 g (0.3982 mol) of p-ch lorophenoI and 55 g I yD4 9 0 24 bromine are then added dropwise at 30°C. The mixture is subsequently stirred at room temperature for 30 minutes and is then concentrated in vacuo. 86.6 g (92% of theory) of crude 2-bromo-prop-2-y I 4-chlorophenyl ketone are obtained and are further reacted directly. The following compounds of the general formula (I) are obtained in a corresponding manner and according to the process described: Ex- ampl( No. R1 R2 3 ch3 4 CHj 5 CHj 6 • ©-CH2- ^■11» ^ CHj 7 0"CH2" CHj 8 CHj 9 CHj 1 0 F-@-CHr ch3 11 F-@^c"r ch3 12 /""C cl^O;-ch2- ch3 13 F-©"CH2- ch3 14 cl-@>-s- ch3 15 f-©-ch2- ch3 16 cing)-s- ch3 ) R5 X T. 1 belting no i nt (0 CHj CH 4-Cl 138 CH, N 4-Cl 137 CHj N 4-Cl 109 CHj N 4-F 120 CHj CH u. 1 118-120 CHj CH 4-F 165-167 CHj N I Tl 124 ch3 ch 4-Cl 126 ch3 n 4-Cl 112 ch3 ch 4-F 93 ch3 CH - 164-65 ch3 n 4-Cl 74-76 ch3 n - 102-04 ch3 CH 4-Cl 94 Example No. Cl-@£ CI ci-(0>-o- r\-a ©■«- ,-ci -0- Cl -<6>o-<§>-0-©-0-ch3-^-O- CH3-@-0- cl-(cVo-chr R2 R3 X Y m Melting point (°C ch3 ch3 CH 4-Cl 80-82 ch3 ch3 N 4-Cl 96-98 ch3 ch3 N 4-Cl 114-16 ch3 ch3 CH 4-Cl 194 ch3 ch3 N 4-Cl 117 ch3 ch3 N 4-Cl 82 ch3 ch3 CH 4-Cl 188 ch3 ch3 N 4-Cl 62 ch3 ch3 CH 4-Cl 106 ch3 ch3 N 4-Cl 104-06 ex - amp I e No . 27 28 29 30 31 32 33 34 35 36 37 -@-CKj L-©-°--®«- -®-o- -@>-ch2 -©-o- ko>-o- I <Q^°- .ci c>°- 2 3 r r x y m Melting Point (°C) c2h5 ch3 ch3 ch3 ch3 ch3 ch3 ch3 ch3 ch3 ch3 ch3 ch3 ch3 c2h5 ch3 c2h5 ch3 ch3 ch3 ch3 ch3 N 4-Cl N 4-F N 4-F N 4-F CH 4-F CH 4-F CH 4-F N 4-F N 4-F m 4-f n 182-84 (x HCl) 118 82 78 154 178 50 114 66 120 14 7 V 7 V - 28 - Use Examples The compounds shown below are used as comparison substances in the examples which follow: OH (A) OCV-(CH3,3 ch2 i ^ N ^ !i - n ^Cl OH (B) Cl-@- C-CH2-0^)CI (!h2 A it ■> (c> <1h, oh ^ CI Ns n ci oh (D) Cl-^/- C -CH2-0-(^)-Cl ch2 I !l N N i oh ci fe) (( j7\{ .}~ c ~ ch 2-yxy- c i ch2 r n^n N 2 2.064 9 C - 29 - Example A Sphaerotheca test (cucumber) / protective Solvent: 4.4 parts by weight of acetone Emulsifier: 0.3 parts by weight of alkylaryl polyglycol 5 ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concen-10 tration. To test for protective activity, young plants are sprayed with the preparation of active compound until dripping wet. After'the spray coating has dried on, the plants are dusted with conidia of the fungus Sphaerotheca 15 fuliginea. The plants are then placed in a greenhouse at 23 to 24°C and at a relative atmospheric humidity of about 75%. Evaluation is carried out 10 days after the 20 inoculation. In this test, a clearly superior activity compared with the prior art is shown, for example, by the compounds according to the following preparation examples: 1, 4, 2, 5, 9, 6, 7, 11, 14 and 18. - 30 -Table A Sphaerotheca test (cucumber) / protective Active compound Infestation in % at an active compound concentration of 50 ppm 5 ppm oh i <SV^C-C(CH3)3 ch2 i (a) l! n (known) ho ci c l-^)-0-ch2-c —^0)-c i ch2 i • ! "I il ' (b) • 1 (known) ' N oh ch2 (C) (known) S"N v I! '' 1 n 100 25 100 ch3 oh ci-@-ch2-c - c-@-Cl ch3 ch2 ^ n "s I '• (1) 20 CH* OH I ' cl-©-ch2-c - c^>cl > dh3 ch2 (4) (f N ■». - 31 -Table A (Continuation) Sphaerotheca test (cucumber) / protective Active compound Infestation in X at an active compound concent rat ion of 5 ppm CH3 OH ci-@-o-c - c-@~ci ch3 ch2 rfN> (2) N L x HCl ch3 oh ci-Ore - c-/c)-ci 0 ch3 ch2 (5) . N U ch3 °h i /• *** cl^5/-ch2-c - c-^j>f 13 ch3 ch2 <9) 'N_jj oh — ch3 , _ <c/-ch2-t - ch3 ch2 (6) N-ii ch3 oh ©-chrc - c-©-f ch3 ch2 c7) /'nn, 10 In II iii Bit - 32 -Table A (Continuation) 206490 Sphaerotheca test (cucumber) / protective Active compound Infestation in % at an active compound concentration of 5 ppm ch3 oh FT^-ch2-C - c-(§rci (11) I I ch3 ch2 /N. ,! N n l 10 ch3 oh ci-Jo^s-c - c-@-ci (14) 10 ch3 ch2 rr^N ■ N Ll ^cl ch3 oh ci-@-o-c - c-@-ci (18) I ch3 ch2 /W- 10 il n N ll ^^49 0 - 33 - Example B Drechslera graminea test (barley) / seed treatment (syn. Helminthosporiurn gramineum) The active compounds are used as dry dressings. 5 These are prepared by extending the particular active compound with a ground mineral to give a finely pulverulent mixture, which ensures uniform distribution on the seed surface. To apply the dressing, the infected seed is 10 shaken with the dressing in a closed glass flask for 3 minutes. •The seed is embedded in sieved, moist standard soil and is exposed to a temperature of 4°C in closed Petri dishes in a refrigerator for 10 days. Germination 15 of the barley, and possibly also of the fungus spores, is thereby initiated. 2 batches of 50 grains of the pre-germinated barley are subsequently sown 3 cm deep in standard soil and are cultivated in a greenhouse at a temperature of about 18°C, in seedboxes which are 20 exposed to light for 15 hours daily. About 3 weeks after sowing, the plants are evaluated for symptoms of stripe disease. In this test, a clearly superior activity compared with the prior art is shown, for example, by the 25 compounds according to the following preparation examples: 6 and 7. - 34 - Table B Orechs Lera graminea test (barley) / seed treatment Csyn. HeLminthosporium gramineum) Active compound Amount of active compoun d applied in mg/kg of seed Diseased pI ant s in X of the total plants erne rged no dressing 25.5 HO CI Cl-@-0CH2-C ' CB) l!—N (known) ho ci CH2 « 500 23-9 Cl-(G/-0CH2~C -\£^-Cl ?h2 500 20.7 CD) N—Ll (known) chj oh CVch2-c - C-'s^-F I : v~' ch3 ch2 (6) . N Ll ch3 oh iP < 7) il- n 500 3-7 #-"2-0 - c-qr' ch3 ch2 500 4,9 - 35 - Example C Leptosphaeria nodorum test (wheat) / protective Solvent: 100 parts by weight of dimethyLformamide Emulsifier: 0.25 parts by weight of alkylaryl polyglycol 5 ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concen-10 tration. To test for protective activity, young plants are sprayed with the preparation of active compound until dew-moist. After the spray coating has dried on, the plants are sprayed with a conidia suspension of Lepto-15 sphaeria nodorum. The plants remain for 48 hours in an incubation cabin at 20°C and 100% relative atmospheric humi dity. The plants are placed in a greenhouse at a temperature of about 15°C and a relative atmospheric 20 humidity of about 80%. Evaluation is effected 10 days after the inoculation. In this test, a clearly superior activity compared with the prior art is shown, for example, by the 25 compounds according to the following preparation examples: 1, 4, 5 and 3. - 36 - Table c 206490 Leptosphaeria nodorum test (wheat) / protective Active compound Active compound concentrat ion in the spray liquor in X by weight Disease infestation in X of the untreated control oh ci <rO)-<j3)-C-CH2-<pvC I 9H2 (E) rf N. I N- N (known) ch3 oh Cl-(0)-ch2-c - c-©-cl ch3 ch2 (1) /Nv |l 'I n ch3 oh I ' /^\ ch2-c - c-<Uvci I I ch3 ch2 1 n (4) N i) CI 0,025 0.-025 0.025 78.5 16.2 16.2 ch3 oh cl-(c^-c - c-^jvci ch3 ch2 -• N- I (5) N N _.J ch3 oh ci^c - c-@-ci (3) ch3 ch2 fi •! ' N 0.025 0.025 37.0 37.0 i ii d 1 ~i a r n - - 37 - Example D Pyricularia test (rice) / protective Solvent: 12.5 parts by weight of acetone Emulsifier: 0.3 parts by weight of alkylaryl polyglycol 5 ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, and the concentrate is diluted with water and the stated amount of emulsifier, 10 to the desired concentration. To test for protective activity, young rice plants are sprayed with the preparation of active compound until dripping wet. After the spray coating has dried off, the plants are inoculated with an aqueous spore sus-15 pension of Pyricularia oryzae. The plants are then placed in a greenhouse at 100% relative atmospheric humidity and 25°C . Evaluation of the disease infestation is carried out 4 days after the inoculation. 20 In this test, a clearly superior activity com pared with the prior art is shown, for example, by the compounds according to the following preparation examples: 7, 15, 18 and 19. </div>

Claims

<div class="application article clearfix printTableText" id="claims"> - 38 - Table D Pyricularia test (rice) / protective Disease infestation in % of the unt reated control Active compounds Active compound concent ration i n % OH I ©"©"^"C(CH3)3 (A) 11—N CH2 0.025 100 (k nown) ch3 oh ! - c 0-025 25 <5vch>-c - c-<(5>- f £h3 ch2 F-^CHj-C - c-vg, CH3 CHj ?Tn'n (15) n u CH3 OH 0.025 25 I ' ^cl ch3 oh Cl-^)-0-C - c-®-Cl 0.025 25 ch3 ch2 (18) /N- f: N n il ci ch3 oh ^Co-c. i _;0Va °-02S 20 ch3 ch2 -s (19) - 39 - WHAT WE CLAIM IS:

1. Fungicidal agents, characterised in that they contain at least one substituted hydroxya Iky l-azole of the general formula •J OH «• - • - f -<gf (I) R3 CH2 N [i in which represents in each case optionally substituted phenyl, -0-phenyl, -S-phenyl, -SO-phenyl, -S02~phenyl, -C^-phenyI, -CH2~0-phenyl, -CH2~S-pheny I, -C^'SO-pheny I or -CH2-SO2-pheny I, R^ represents alkyl, R3 represents alkyl, X represents a nitrogen atom or the CH group, Y represents halogen, alkyl, cycloalkyl, alkoxy, alkylthio, halogenoa Iky I, ha logenoa Ikoxy, halo-genoaIkyIthio, optionally substituted phenyl, optionally substituted phenoxy, optionally substituted phenylalkyl or optionally substituted phenylalkoxy and m represents the number 0, 1, 2 or 3, and/or its acid addition salts and metal salt complexes.

2. Fungicidal agents of the general formula (I) in Claim 1, wherein represents phenyl, -CH2~phenyl, -CH2~0~pheny I, -CH2-S-pheny I, -C^-SO-phenyl or C H2-S02-pheny I, in each case mono- or di-substituted by identical or different substituents, substituents on the phenyl being selected from the meanings " - of Y given below; / ^ C^ (n 'Z16 MAY1986 O , r *06490 - 40 - 2 Rfc represents straight-chain or branched alkyl with 1 to 4 carbon atoms; R3 represents straight-chain or branched alkyl with 1 to 4 carbon atoms; X represents a nitrogen atom or the CH group; Y represents halogen, alkyl with 1 to 4 carbon atoms, cycloalkyl with 5 to 7 carbon atoms, alkoxy or alkylthio with in each case 1 to 4 carbon atoms, halogenoa Iky I, halogenoaIkoxy or halogenoa Iky Ithio with in each case 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms, or phenyl, phenoxy or phenylalkyl or phenylalkoxy with 1 or 2 carbon atoms in the alkyl part or in the alkoxy part, each of which is optionally substituted by halogen or alkyl with 1 or 2 carbon atoms, and m represents the number 0, 1, 2 or 3.

3. Fungicidal agents of the general formula (I) in Claim 1, wherein represents -0-phenyl, -S-phenyl, -SO-phenyl or -S02~phenyl/ in each case mono- or di-sub-stituted by identical or different substituents, substituents on the phenyl being selected from the meanings of Y given below; represents straight-chain or branched alkyl with 1 to 4 carbon atoms; R3 represents straight-chain or branched alkyl with 1 to 4 carbon atoms; X represents a nitrogen atom or the CH group; Y represents halogen, alkyl with 1 to 4 carbon atoms, cycloalkyl with 5 to 7 carbon atoms, alkoxy or alkylthio with in each case 1 to 4 carbon atoms, halogenoa Iky I, halogenoa Ikoxy or halogenoa IkyIthio with in each case 1 or 2 carbon atoms and 1 to 5 identical or di f f erentJia logen r* ■■ ~~ - ' > A-aa Biift V* •V • ; I 306490 - 41 - atoms, or phenyl, phenoxy or phenylalkyl or phenylalkoxy with 1 or 2 carbon atoms in the alkyl part or in the alkoxy part, each of which is optionally substituted by halogen or alkyl with 1 or 2 carbon atoms; and m represents the number 0, 1, 2 or 3.

4. Fungicidal agents of the general formula CI) in Claim 1, wherein represents phenyl, -CH2-phenyl, -CH2-0-pheny I, -CH2-S-pheny I, -CH2-SO-phenyI or -CH2-S02~pheny I, in each case mono- or di-substituted by identical or different substituents, substituents on the phenyl being selected from those meanings of Y given below; represents methyl or ethyl; R3 represents methyl or ethyl; X represents a nitrogen atom or the CH group; Y represents fluorine, chlorine, bromine, methyl, isopropyl, tert.-butyl, cyclohexyl, methoxy, methylthio, trif luoromethyI, trif luoromethoxy or trifluoromethylthio, or phenyl, phenoxy, benzyl or benzyloxy which is optionally substituted by fluorine, chlorine or methyl; and m represents the number 0, 1 or 2.

5. Fungicidal agents of the general formula CI) in Claim 1, wherein R^ represents -0-phenyl, -S-phenyl, -SO-phenyl or -S02"phenyl, in each case mono- or di-sub-stituted by identical or different substituents, substituents on the phenyl being selected from those meanings of Y given below; 2 R represents methyl or ethyl, R3 represents methyl or ethyl; 2064 90 - 42 - Y represents fluorine, chlorine/ bromine, methyl, isopropyl, tert.-butyl, cyclohexyl, methoxy, methylthio, trifluoromethyI, trifIuoromethoxy or trifIuoromethyIthio, or phenyl, phenoxy, benzyl or benzyloxy which is optionally substituted by fluorine, chlorine or methyl, and m represents the number 0, 1 or 2.

6. Method of combating fungi, characterised in that s ub s t i t u t e d hydroxya I kyI-azoIes of the formula (I) i n Claim 1 are allowed to act on fungi or their environment 7. Use of substituted hyo'roxyalkyl-azoles of the f o r muI a (I) in Claim 1 as plant protection agents. 8. Use of substituted hydroxyalkyl-azoles of the f o r muI a (I) in Claim 1 for combating fungi.

9. Process for the preparation of fungicidal agents, characterised in that substituted hydroxyalkyl-azoles of the formula (I) in Claim 1 are mixed with extenders and/ or surface-active agents.

10. A fungicidal agent according to claim 1 substantially as herein described or exemplified. BAYER AKTIENGESELLSCHAFT By Their Attorneys HENRY HUGHES LIMITED By: j j mi. i A DP 0 6 0' </div>